JP5445215B2 - Active energy ray-curable resin composition, cured film and laminate - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate oligomer, a cured film obtained by irradiating the composition with active energy rays, and a laminate having the same.

Conventionally, radical polymerization type active energy ray-curable resin compositions are cured in a short time by irradiation with active energy rays, and provide films and molded products with excellent scratch resistance, chemical resistance, contamination resistance, etc. Therefore, it is widely used in various surface processing fields and cast molded product applications.
Above all, from the viewpoint of curability and work efficiency, the active energy ray-curable resin composition is preliminarily cured to create a resin sheet, which is subjected to surface processing and the like, and then subjected to three-dimensional processing at room temperature or under heating conditions. Although the method is used, in this case, the active energy ray-curable resin sheet needs flexibility and elongation to follow deformation during three-dimensional processing.

As such a resin sheet, Patent Document 1 discloses an active energy ray-curable resin laminate that exhibits a specific elongation at break and has a cured layer of a composition containing a urethane (meth) acrylate oligomer. .
On the other hand, Patent Document 2 discloses a decorative sheet for building materials that is a cured product of a resin composition made of urethane acrylate, and is said to be excellent in contamination resistance, which is a characteristic required for a surface-protective resin sheet. ing.
JP 2007-30479 A JP 2001-129938 A

  However, although the active energy ray-curable resin laminate described in Patent Document 1 has good elongation at break and strength at elongation and is excellent in three-dimensional workability, it is inferior in stain resistance as a surface protective resin sheet. It is. In addition, the laminate described in Patent Document 1 exhibits desired characteristics by having two or more resin layers having different characteristics, and a simple resin sheet cannot be produced by single-layer coating. There is a problem that the film thickness is limited.

The decorative sheet for building materials described in Patent Document 2 does not have flexibility and elongation enough to follow the deformation of three-dimensional processing, and is inferior in three-dimensional workability even under high temperature conditions.
The present invention has been made to solve the above-mentioned problems, and a cured film obtained by curing can follow the deformation during three-dimensional processing under high temperature conditions, flexibility at break, mechanical strength An object of the present invention is to provide an active energy ray-curable resin composition that has both strength and stain resistance against general household contaminants such as ink and ethanol.

  In addition, a cured film obtained by curing such a composition and a laminate having a layer formed of the cured film on the surface, and a cured film capable of imparting design properties or surface protection to various substrates, and the cured film Another object of the present invention is to provide a laminate having a layer made of

  As a result of intensive studies to achieve the above-mentioned object, the present inventor is an active energy ray-curable resin composition containing a urethane (meth) acrylate oligomer (A) having a specific structure, which is calculated in the composition. The active energy ray-curable resin composition having a molecular weight between cross-linking points of 1000 to 6000 is a cured film obtained by curing the active energy ray curable resin composition at the time of three-dimensional processing under higher temperature conditions than those conventionally known. The present invention has been found out to be particularly excellent in flexibility capable of following deformation, elongation at break, mechanical strength, and stain resistance.

That is, the present invention provides an isocyanate-terminated urethane by reacting at least (a-1) a polyisocyanate and (a-2) a low molecular weight polyol having a number average molecular weight of 500 or less having an alicyclic structure so that the isocyanate group becomes excessive. An active energy ray-curable resin composition comprising a urethane (meth) acrylate oligomer (A) obtained by obtaining a prepolymer and then reacting the isocyanate-terminated urethane prepolymer with (a-3) hydroxyalkyl (meth) acrylate a ones, calculated in (a-2) as the number average molecular weight of 500 or lower molecular weight polyol having an alicyclic structure includes 1,4-cyclohexanedimethanol, and the active energy ray curable resin sets Narubutsu Active energy having a molecular weight between network cross-linking points of 1000 or more and 6000 or less It relates to a curable resin composition.

Moreover, this invention relates to the said active energy ray curable resin composition in which the said (a-1) polyisocyanate contains the polyisocyanate which has an alicyclic structure.
Further, the present invention provides a three-component total amount of (a-1) polyisocyanate, (a-2) a low molecular weight polyol having an alicyclic structure and having a number average molecular weight of 500 or less, and (a-3) hydroxyalkyl (meth) acrylate. Is 100.0 mol%, (a-2) the number average molecular weight 500 or less low molecular weight polyol having an alicyclic structure is 15.0 mol% or more and 42.5 mol% or less, and (a -3) The said active energy ray-curable resin composition whose hydroxyalkyl (meth) acrylate is 7.5 mol% or more and 35.0 mol% or less .

The present invention also provides (a-1) a polyisocyanate in which the alicyclic structure of the polyisocyanate has a six-membered ring structure, and the six-membered ring structure between isocyanato groups is bonded by 1,4-position substitution. It contains the said active energy ray curable resin composition containing.
The present invention also relates to the active energy ray-curable resin composition, wherein the urethane (meth) acrylate oligomer (A) is a reaction product further comprising (a-5) a high molecular weight polyol having a number average molecular weight of more than 500. .

Furthermore, this invention relates also to the cured film formed by irradiating the said active energy ray curable resin composition with an active energy ray.
Furthermore, this invention relates also to the laminated body which has a layer which consists of the said cured film on a base material.

  When the active energy ray-curable resin composition of the present invention is cured to form a cured film, the flexibility, elongation at break, mechanical strength capable of following deformation during three-dimensional processing under high temperature conditions, In addition, a cured film having stain resistance against general household contaminants such as ink and ethanol can be provided at the same time, and by using the cured film as a coating on various substrates, it is possible to impart designability or surface protection. it can.

  That is, the active energy ray-curable resin composition of the present invention can provide a cured film having excellent three-dimensional moldability and good stain resistance, such as various processed product fields and cast molded products. It can be widely used for applications. Moreover, it is expected that the active energy ray-curable resin composition of the present invention can easily produce a thin film-like resin sheet by applying a single layer.

In the following, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. .
In this specification, (meth) acrylate is a general term for acrylate and methacrylate. The same applies to the (meth) acryloyl group and (meth) acrylic acid.

Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.
Molecular weight between calculated network crosslink points The active energy ray-curable resin composition of the present invention is characterized in that the molecular weight between calculated network crosslink points is 1000 to 6000.

  In the present specification, the molecular weight between the calculated network crosslinking points of the composition is the average of the molecular weights between the active energy ray reactive groups (hereinafter sometimes referred to as crosslinking points) that form the network structure in the entire composition. Represents. The molecular weight between the calculated network crosslinking points correlates with the network area at the time of forming the network structure, and the larger the calculated molecular weight between the crosslinking points, the lower the crosslinking density. In the reaction by active energy ray curing, when a compound having only one active energy ray reactive group (hereinafter sometimes referred to as a monofunctional compound) reacts, it becomes a linear polymer, while the active energy ray reaction. When a compound having two or more groups (hereinafter sometimes referred to as a polyfunctional compound) reacts, a network structure is formed. Therefore, the active energy ray reactive group of the polyfunctional compound is a crosslinking point, and the calculation of the molecular weight between the calculated network crosslinking points is centered on the polyfunctional compound having the crosslinking point, and the monofunctional compound has the polyfunctional compound. The molecular weight between the crosslinking points is treated as having an effect of extending the molecular weight, and the molecular weight between the calculation network crosslinking points is calculated. In addition, the calculation of the molecular weight between the calculation network crosslinking points is performed on the assumption that all the active energy ray reactive groups have the same reactivity and that all the active energy ray reactive groups react by irradiation with the active energy ray. .

In a polyfunctional compound single-system composition in which only one kind of polyfunctional compound reacts, the molecular weight between calculated network crosslinking points is twice the average molecular weight per active energy ray reactive group of the polyfunctional compound. For example, (1000/2) × 2 = 1000 for a bifunctional compound with a molecular weight of 1000, and (300/3) × 2 = 200 for a trifunctional compound with a molecular weight of 300.
In a polyfunctional compound mixed system composition in which multiple types of polyfunctional compounds react, the average value of the molecular weights between the calculated network cross-linking points of each of the above single systems with respect to the total number of active energy ray reactive groups contained in the composition is This is the molecular weight between the calculated network crosslinking points of the composition. For example, in a composition comprising a mixture of 4 moles of a bifunctional compound having a molecular weight of 1000 and 4 moles of a trifunctional compound having a molecular weight of 300, the total number of active energy ray reactive groups in the composition is 2 × 4 + 3 × 4 = 20. The molecular weight between the calculated network cross-linking points of the composition is {(1000/2) × 8 + (300/3) × 12} × 2/20 = 520.

  When a monofunctional compound is included in the composition, a molecular chain formed by calculation and equimolar to the active energy ray reactive group (that is, the crosslinking point) of the polyfunctional compound, and the monofunctional compound linked to the crosslinking point Assuming that the reaction takes place in the middle of the molecular chain, the elongation of the molecular chain by the monofunctional compound at one crosslinking point is the total molecular weight of the monofunctional compound, the total number of reactive energy reactive groups of the polyfunctional compound in the composition Half of the value divided by. Here, since the molecular weight between the calculated network cross-linking points is considered to be twice the average molecular weight per cross-linking point, the amount extended by the monofunctional compound relative to the calculated molecular weight between the cross-linking points calculated for the polyfunctional compound is The value obtained by dividing the total molecular weight of the monofunctional compound by the total number of reactive energy ray reactive groups of the polyfunctional compound in the composition. For example, in a composition comprising a mixture of 40 mol of a monofunctional compound having a molecular weight of 100 and 4 mol of a bifunctional compound having a molecular weight of 1000, the number of reactive energy ray reactive groups of the polyfunctional compound is 2 × 4 = 8. The extension due to the monofunctional compound in the molecular weight between the network crosslinking points is 100 × 40/8 = 500. That is, the molecular weight between calculated network crosslinks of the composition is 1000 + 500 = 1500.

From the above, in the mixture of monofunctional compounds M _A molar molecular weight W _A, and f _B functional compound M _B mol molecular weight W _B, and f _C functional compound M _C mol molecular weight W _C, the composition The molecular weight between the calculated network cross-linking points of the product can be expressed by the following formula.

The molecular weight between calculated network crosslinking points of the active energy ray-curable resin composition of the present invention is 1000 or more, preferably 1500 or more, more preferably 2000 or more, and 6000 or less, preferably 5500 or less, more preferably 4800 or less. It is.
It is preferable that the molecular weight between the calculated network crosslinking points is not more than the upper limit value because the cured film obtained from the composition has good stain resistance and tends to have a good balance between three-dimensional processability and stain resistance. Moreover, it is preferable that the molecular weight between the calculated network cross-linking points is equal to or more than the lower limit because the resulting cured film has good three-dimensional workability and tends to have an excellent balance between three-dimensional workability and stain resistance. This is because the three-dimensional workability and stain resistance depend on the distance between the cross-linking points in the network structure. When this distance is increased, the structure becomes flexible and easily stretched, and the three-dimensional processability is excellent. This is presumed to be because the structure becomes a strong structure and is excellent in stain resistance.

Urethane (meth) acrylate oligomer (A)
The active energy ray-curable resin composition of the present invention contains a urethane (meth) acrylate oligomer (A). The urethane (meth) acrylate oligomer (A) used in the present invention is a compound having one or more radically polymerizable (meth) acryloyl groups and at least two urethane bonds in the molecule. Urethane (meth) acrylate oligomer (A) has a balanced tensile strength and excellent tensile elongation when cured by irradiation with active energy rays, and is excellent in surface curability as a composition. It is superior to other typical active energy ray-curable oligomers such as epoxy (meth) acrylate oligomers, acrylic (meth) acrylate oligomers, and the like because they are difficult to remain.

  The urethane (meth) acrylate oligomer (A) comprises (a-1) polyisocyanate, (a-2) a low molecular weight polyol having a number average molecular weight of 500 or less having an alicyclic structure, (a-3) hydroxyalkyl (meta ) A reaction product of acrylate. In addition, as long as the effects of the present invention are not impaired, (a-4) a low-molecular weight polyol having a number average molecular weight of 500 or less and / or (a-5) a high-molecular weight polyol exceeding the number average molecular weight of 500, which does not have an alicyclic structure. A reaction product containing

Below, each component of (a-1)-(a-5) is demonstrated.
(A-1) Polyisocyanate The polyisocyanate as the component (a-1) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule. (A-1) Specific examples of the polyisocyanate include aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate; bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (Isocyanatocyclohexyl) diisocyanates having an alicyclic structure such as methane and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, naphthalene diisocyanate; tris (isocyanatohexyl) isocyanate Aliphatic triisocyanates such as nurate, tris (isocyana Triisocyanate and the like having an alicyclic structure isophorone) isocyanurate, may be used these alone, or may be used in combination of two or more kinds.

  From the viewpoint of mechanical strength and stain resistance of a cured product obtained by curing the active energy ray-curable resin composition of the present invention, (a-1) the polyisocyanate contains a polyisocyanate having an alicyclic structure. It is more preferable to include an isocyanate group and / or a polyisocyanate having two or more substituents containing the isocyanate group in the alicyclic structure, and the two isocyanate groups are in symmetrical positions across the alicyclic structure. It is particularly preferred that it is present. That is, when the alicyclic structure is a 6-membered ring, it is preferable that the 6-membered ring structure between the isocyanato groups is bonded by 1,4-position substitution. For example, a polyisocyanate having an isocyanato group and / or a substituent containing an isocyanato group at the 1,4-position, or a compound having two six-membered ring structures, and the isocyanato at the 4,4′-position of the six-membered ring structure It is particularly preferable to include a polyisocyanate having a substituent containing a group and / or an isocyanato group.

  Examples of the substituent containing an isocyanate group include an alkyl group having 1 to 5 carbon atoms, an alkenyl group, and an alkoxyl group containing one or more isocyanate groups. The isocyanato group and / or the isocyanato group-containing substituent having an alicyclic structure is preferably an isocyanato group, or an alkyl group having 1 to 3 carbon atoms, an alkenyl group or an alkoxyl group, more preferably one isocyanato group. Includes an isocyanato group or an alkyl group having 1 to 3 carbon atoms including one isocyanato group.

The isocyanato group containing an alicyclic structure and / or the substituent containing the isocyanato group may be the same or different.
Specifically, bis (isocyanatomethyl) cyclohexane, cyclohexane diisocyanate, bis (isocyanatocyclohexyl) are preferred in applications where the weather resistance of a cured product obtained by curing the active energy ray-curable resin composition is required. ) Aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate are preferred in applications where methane and diisocyanate having an alicyclic structure such as isophorone diisocyanate and the mechanical strength of the cured product is required.
(A-1) The number average molecular weight of the polyisocyanate is 100 or more, more preferably 150 or more in terms of the balance between strength and elastic modulus as a cured product obtained by curing the active energy ray-curable resin composition. Preferably, it is 1,000 or less, more preferably 500 or less.

(A-2) Low molecular weight polyol having a number average molecular weight of 500 or less having an alicyclic structure Low molecular weight polyol having a number average molecular weight of 500 or less having an alicyclic structure as component (a-2) is 2 in one molecule. The compound is not particularly limited as long as it is a compound having at least one hydroxyl group and having an alicyclic structure and a number average molecular weight of 500 or less, but preferably has two or more substituents containing a hydroxyl group in the alicyclic structure.

  Among them, a low molecular weight polyol in which at least two hydroxyl groups are present at symmetrical positions across the alicyclic structure is preferable. That is, when the alicyclic structure is a six-membered ring, the six-membered ring between the hydroxyl groups is preferred. It is preferred that the structures are linked by 1,4-position substitution. For example, a low molecular weight polyol having a hydroxyl group and / or a substituent containing a hydroxyl group at the 1,4-position, or a compound having two six-membered ring structures, wherein the hydroxyl group is located at the 4,4′-position of the six-membered ring structure. It is particularly preferred to include low molecular weight polyols having substituents containing groups and / or hydroxyl groups.

  As a substituent containing a hydroxyl group, a C1-C5 alkyl group, an alkenyl group, an alkoxyl group etc. which contain a 1 or more hydroxyl group are mentioned, for example. The hydroxyl group and / or the substituent containing the hydroxyl group in the alicyclic structure is preferably a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, an alkenyl group, or an alkoxyl group, and more preferably one hydroxyl group. Is a C1-C3 alkyl group containing a hydroxyl group or one hydroxyl group.

These hydroxyl groups and / or substituents containing hydroxyl groups may all be the same or different.
Specific examples of the component (a-2) include cyclopropanediol, cyclopropanedimethanol, cyclopropanediethanol, cyclopropanedipropanol, cyclopropanedibutanol, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, Cyclopentanedipropanol, cyclopentanedibutanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, cyclohexanedipropanol, cyclohexanedibutanol, cyclohexenediol, cyclohexenedimethanol, cyclohexenediethanol, cyclohexenedipropanol, cyclohexenedibutanol, cyclohexadienediol, Cyclohexadiene dimethanol, cyclohexadi Diethanol, cyclohexadiene dipropanol, cyclohexadiene dibutanol, hydrogenated bisphenol A, tricyclodecane diol, adamantyl diol, and the like. These may be used alone or in combination of two or more. It may be used.

  Among these, in applications where the mechanical strength of a cured product obtained by curing the active energy ray-curable resin composition and the stain resistance are required, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, Two hydroxyl groups such as 1,4-cyclohexanediethanol, 1,4-cyclohexanedipropanol, 1,4-cyclohexanedibutanol, hydrogenated bisphenol A and the like are present at symmetrical positions across the alicyclic structure. Preferably it contains a molecular weight polyol. This is presumably because such a low molecular weight polyol has less steric hindrance, so that the packing effect at the time of crystal structure formation when the resulting composition is cured is increased, resulting in a stronger structure. The Particularly preferred are 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

From the viewpoint of mechanical strength characteristics and contamination resistance, the number average molecular weight of 500 or less, having a hydroxyl group at positions 1 and 4 of the alicyclic structure of 50 mol% or more, and further 75 mol% or more in component (a-2). It is preferable to use a low molecular weight polyol of 100 mol% of the component (a-2).
(A-2) The number average molecular weight of a low molecular weight polyol having an alicyclic structure and having a number average molecular weight of 500 or less is the elongation and elasticity as a cured product obtained by curing the active energy ray-curable resin composition. In view of the balance, it is preferably 100 or more, and on the other hand, it is preferably 300 or less.

(A-3) Hydroxyalkyl (meth) acrylate If the hydroxyalkyl (meth) acrylate which is a component (a-3) is a compound which has one or more hydroxyl groups and one or more (meth) acryloyl groups together, There is no particular limitation. As the component (a-3), specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Cyclohexanedimethanol mono (meth) acrylate, addition reaction product of 2-hydroxyethyl (meth) acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth) acrylate and caprolactone, glycidyl ether and (meth) acrylic acid Addition reaction products, glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc., and one of these may be used alone, Combine more than seeds It may be used Te. Among the above, hydroxy having 2 to 4 carbon atoms between the hydroxyl group and the ester bond derived from acrylic such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. Alkyl (meth) acrylates are particularly preferred from the viewpoint of mechanical strength of the resulting cured film.

(A-3) The number average molecular weight of the hydroxyalkyl (meth) acrylate is preferably 40 or more, more preferably 80 or more, and from the viewpoint of mechanical strength of the resulting cured film, 800 or less, and further 400 or less. Is preferred.
In the urethane (meth) acrylate oligomer (A) according to the present invention, components other than the above components (a-1) to (a-3) may be used as long as the effects of the present invention are not impaired. Examples of such components include (a-4) a low molecular weight polyol having a number average molecular weight of 500 or less having no alicyclic structure, (a-5) a high molecular weight polyol having a number average molecular weight of more than 500, a polyolefin polyol, and silicon. Examples include polyols and chain extenders.

(A-4) Number average molecular weight 500 or less low molecular weight polyol having no alicyclic structure The number average molecular weight 500 or less low molecular weight polyol not having an alicyclic structure which is component (a-4) is specifically Is, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2, 2,4-trimethyl-1,5-pentanediol, 2,3,5-trimethyl-1,5-pentane Diol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 3,3-dimethylolheptane, 1,8-octanediol, Aliphatic diols such as 2-methyl-1,8-octanediol and 1,9-nonanediol; aromatic diols such as bishydroxyethoxybenzene, bishydroxyethyl terephthalate and bisphenol-A; Examples include alkanolamines; pentaerythritol, sorbitol, mannitol, glycerin, trimethylolpropane and the like. One of these may be used alone, or two or more may be used in combination.

  Among these, aliphatic diols are preferred from the viewpoint of the weather resistance of the cured film obtained. In particular, in applications where the mechanical strength of the cured product is required, ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, Particularly preferred are polyols having 1 to 4 carbon atoms between hydroxyl groups, such as 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol.

  (A-4) The number average molecular weight of 500 or less having no alicyclic structure is the balance between the elongation and the elastic modulus as a cured product obtained by curing the active energy ray-curable resin composition. In view of this, it is preferably 50 or more, on the other hand, preferably 250 or less, particularly preferably 150 or less.

(A-5) High molecular weight polyol having a number average molecular weight exceeding 500 The high molecular weight polyol having a number average molecular weight exceeding 500 as the component (a-5) is specifically, for example, polyether diol, polyester diol, polyether ester diol. And polycarbonate diol.
Examples of the polyether diol include those obtained by ring-opening polymerization of a cyclic ether, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Polyester diols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, etc.) or anhydrides thereof and low molecular weight diols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylolheptane, 1,9- Nonanediol, 2-methyl-1,8-o Tandiol, cyclohexanedimethanol, bishydroxyethoxybenzene, etc.), such as polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene sebacate, etc. Examples thereof include those obtained by ring-opening polymerization such as polycaprolactone and polymethylvalerolactone.

Examples of the polyether ester diol include those obtained by ring-opening polymerization of a cyclic ether to a polyester diol, those obtained by polycondensation of a polyether diol and the above dicarboxylic acid, such as poly (polytetramethylene ether) adipate.
Examples of the polycarbonate diol include polybutylene carbonate, polyhexamethylene carbonate, poly (3-methyl-1,5-pentylene) carbonate obtained by deglycolization or dealcoholization from the above low molecular weight diol and alkylene carbonate or dialkyl carbonate, and the like. And the like.

Among these, polycarbonate glycol is preferable from the viewpoint of weather resistance and mechanical strength of a cured product obtained by curing the active energy ray-curable resin composition.
(A-5) The number average molecular weight of the polymer polyol is preferably 10,000 or less, more preferably 5000 or less, and particularly preferably 2000 or less. When the number average molecular weight is smaller than this, the workability is good without significantly increasing the viscosity of the urethane (meth) acrylate oligomer, and the cured product obtained by curing the active energy ray-curable resin composition is mechanical. This is preferable because strength and stain resistance tend to be improved.

Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol.
Examples of the silicon polyol include polydimethylsiloxane polyol.
Specific examples of the chain extender include aromatic diamines such as 2,4- or 2,6-tolylenediamine, xylylenediamine, and 4,4′-diphenylmethanediamine; ethylenediamine and 1,2-propylene. Diamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 2,2,4- or 2,4,4-trimethylhexanediamine, Aliphatic diamines such as 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, and 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethanediamine (hydrogenated MDA), isopropylidene Low molecular weight diamine compounds having a number average molecular weight of 500 or less, such as alicyclic diamines such as rohexyl-4,4′-diamine, 1,4-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, tricyclodecanediamine, and the like. It is done. These chain extenders may be used individually by 1 type, and may be used in combination of 2 or more type.
The number average molecular weights such as (a-1) to (a-5) described above are calculated from the chemical formula for those other than the polyol having a molecular weight distribution in a gel permeation chromatogram (hereinafter abbreviated as GPC). Moreover, about the polyol which has molecular weight distribution by GPC, it calculated | required by OH value.

<Calculation of number average molecular weight by GPC>
Using GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), tetrahydrofuran as a solvent, polystyrene as a standard sample, TSK gel superH1000 + H2000 + H3000 as a column, liquid feeding speed 0.5 cm ³ / min, column oven temperature 40 ° C. The number average molecular weight is measured.

<Calculation of number average molecular weight of polyol by OH number>
Into an Erlenmeyer flask, 2 g of polyol and 0.5 mol / liter of a phthalic anhydride pyridine solution are reacted at 100 ° C. for 2 hours, and then diluted with 150 cm ³ of acetone. Thereafter, it is titrated with a 0.5 mol / liter sodium hydroxide aqueous solution. Further, except that no polyol was added to the Erlenmeyer flask, titration was performed in the same manner to obtain a blank, and the number average molecular weight was calculated by the following formula.

OH value = {(BA) × 0.5 × 56.11 × 1000} / 2 × 1000
A: Amount of aqueous sodium hydroxide solution required for titration of polyol-containing solution B: Amount of aqueous sodium hydroxide solution required for titration of blank solution not containing polyol Number average molecular weight of polyol = {(56.11 × 1000) / OH value} × number of functional groups The amount of total isocyanate groups and the amount of total hydroxyl groups in the urethane (meth) acrylate oligomer (A) according to the present invention are usually equimolar in theory.

  The amount of all acrylate groups in the urethane (meth) acrylate oligomer (A) according to the present invention is usually 15 mol% or more, preferably 25 mol% or more, and usually 70 mol%, based on the amount of all polyols. Hereinafter, it is preferably 50 mol% or less. According to this ratio, the molecular weight of the urethane (meth) acrylate oligomer (A) to be obtained can be controlled. When the proportion of acrylate groups is large, the molecular weight tends to decrease, and when the proportion of acrylate groups is small, the molecular weight tends to increase.

  Regarding the relative amount ratio of the three components (a-1), (a-2), and (a-3), when the total amount of the three components is 100.0 mol%, the component (a-1) 50.0 Component (a-2) is preferably 15.0 mol% or more, more preferably 25.0 mol% or more, and preferably 42.5 mol% or less, relative to mol%. More preferably, it is 37.5 mol% or less, and component (a-3) is preferably 7.5 mol% or more, more preferably 12.5 mol% or more, It is preferably 35.0% by mole or less, and more preferably 25.0% by mole or less.

  When the urethane (meth) acrylate oligomer (A) contains a low molecular weight polyol having a number average molecular weight of 500 or less (a-4) having no alicyclic structure, (a-2) a number average having an alicyclic structure Component (a-2) based on the total amount of low molecular weight polyol having a number average molecular weight of 500 or less, which is a combination of a low molecular weight polyol having a molecular weight of 500 or less and (a-4) a low molecular weight polyol having a number average molecular weight of 500 or less having no alicyclic structure. ) Is preferably 40 mol% or more, more preferably 60 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, and 95 mol % Or more is most preferable. The upper limit is usually 100 mol%. When the amount of the component (a-2) is larger than the lower limit, the stain resistance tends to be good, which is preferable. This is presumably because the chain structure having an alicyclic structure is easily arranged when the cured product is formed, and the crystallinity is increased.

  When the urethane (meth) acrylate oligomer (A) contains a high molecular weight polyol (a-5) having a number average molecular weight exceeding 500, the low molecular weight polyol having a number average molecular weight of 500 or less and a high molecular weight polyol having a number average molecular weight exceeding 500 are used. And the total amount of polyol ((a-2) + (a-4) + (a-5)) with respect to the total amount of low-molecular weight polyol having a number average molecular weight of 500 or less ((a-2) + (a− 4)) is preferably 30 mol% or more, more preferably 50 mol% or more, and the upper limit is usually 100 mol%. When the amount ((a-2) + (a-4)) of the low molecular weight polyol having a number average molecular weight of 500 or less is larger than the lower limit value, the mechanical strength and the stain resistance tend to be improved. This is presumably because the use of a low molecular weight polyol improves the hydrogen bonding ability between the urethane bonds of the urethane (meth) acrylate oligomer (A), resulting in a stronger structure.

  The amount of the components (a-1) to (a-3) relative to the urethane (meth) acrylate oligomer (A) is preferably 60 mol% or more, more preferably 70 mol% or more, and 80%. It is especially preferable to set it as mol or more, and it is most preferable to set it as 90 mol% or more.

Production method of urethane (meth) acrylate oligomer (A) The urethane (meth) acrylate oligomer (A) according to the present invention is a number having (a-2) an alicyclic structure in (a-1) polyisocyanate. It can be produced by addition reaction of a low molecular weight polyol having an average molecular weight of 500 or less and (a-3) hydroxyalkyl (meth) acrylate. Here, (a-4) a low molecular weight polyol having a number average molecular weight of 500 or less having no alicyclic structure, (a-5) a high molecular weight polyol exceeding the number average molecular weight of 500, a polyolefin polyol silicone polyol, a chain extender, etc. When used in combination, (a-1) polyisocyanate, (a-2) a low molecular weight polyol having an alicyclic structure and a number average molecular weight of 500 or less, (a-3) hydroxyalkyl (meth) acrylate, (a- 4) Manufactured by addition reaction of a low molecular weight polyol having a number average molecular weight of 500 or less having no alicyclic structure, (a-5) a high molecular weight polyol having a number average molecular weight of more than 500, a polyolefin polyol silicone polyol, a chain extender and the like. can do.

These addition reactions can be performed by any known method. For example, the following methods (1) to (3) may be mentioned.
(1) Isocyanate-terminated urethane prepolymer obtained by reacting components other than component (a-3) under conditions such that the isocyanato group becomes excessive, and then the isocyanate-terminated urethane prepolymer and component (a-3) A prepolymer method in which is reacted. (2) One-shot method in which all components are added simultaneously and reacted. (3) After reacting component (a-1) and component (a-3) first, and synthesizing a urethane (meth) acrylate prepolymer having a (meth) acryloyl group and an isocyanato group in the molecule at the same time, Examples thereof include a method of reacting a component other than the component (a-1) and the component (a-3). Of these, the method (1) is preferred because the molecular weight can be controlled and acryloyl groups can be introduced at both ends.

  The addition reaction catalyst at this time is not particularly limited as long as the effect of the present invention is not impaired. For example, dibutyltin laurate, dibutyltin dioctoate, dioctyltin dilaurate, dioctyltin dioctoate and the like are preferable. They may be used alone or in combination of two or more. Of these, dioctyltin dilaurate is preferred.

Moreover, let the preparation ratio of each component be a ratio used as the composition of the urethane (meth) acrylate oligomer (A) according to the present invention described above. Specifically, the charging ratio of each component is usually the same as the composition of the urethane (meth) acrylate oligomer (A) according to the present invention described above.
In the active energy ray-curable resin composition of the present invention, an active energy ray-reactive monomer other than the urethane (meth) acrylate oligomer (A), active energy ray-curing property, if necessary, as long as the effects of the present invention are not impaired. An oligomer, a polymerization initiator, a light enhancer, an additive, and the like may be included.

Active energy ray-reactive monomer other than urethane (meth) acrylate oligomer (A) As active energy ray-reactive monomer other than urethane (meth) acrylate oligomer (A), known as long as the effects of the present invention are not significantly impaired. Any active energy ray-reactive monomer can be used. These active energy ray reactive monomers are intended to adjust the hydrophilicity / hydrophobicity of the urethane (meth) acrylate oligomer (A) and the physical properties such as hardness and elongation of the cured product when the resulting composition is a cured product. Used in etc.
Examples of such active energy ray-reactive monomers include compounds such as vinyl ethers, (meth) acrylamides, and (meth) acrylates. Specifically, for example, aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N -Vinyl ester monomers such as vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; Vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; Allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether and allyl glycidyl ether; Acrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-butyl (Meth) acrylamides such as acrylamide, acryloylmorpholine, methylenebisacrylamide; (meth) acrylic acid, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid n -Butyl, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) Glycidyl acrylate, dimethylameth (meth) acrylate Noethyl, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acrylic acid dicyclopentenyloxyethyl, (meth) acrylic acid dicyclopentanyl, (meth) acrylic acid allyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid isobornyl, (meth) acrylic acid Monofunctional (meth) acrylates such as phenyl; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di (meth) Acrylic acid polyethylene Glycol (n = 5-14), propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, di (Meth) acrylic acid polypropylene glycol (n = 5-14), di (meth) acrylic acid 1,3-butylene glycol, di (meth) acrylic acid 1,4-butanediol, di (meth) acrylic acid polybutylene glycol (N = 3 to 16), di (meth) acrylic acid poly (1-methylbutylene glycol) (n = 5 to 20), di (meth) acrylic acid 1,6-hexanediol, di (meth) acrylic acid 1 , 9-nonanediol, neopentyl glycol di (meth) acrylate, neopentyl hydroxypivalate Recall di (meth) acrylic acid ester, di (meth) acrylic acid dicyclopentanediol, di (meth) acrylic acid tricyclodecane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate , Trimethylolpropane trioxypropyl (meth) acrylate, trimethylolpropane polyoxyethyl (meth) acrylate, trimethylolpro Polyoxypropyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, Ethylene oxide-added building phenol F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, bisphenol A epoxy di (meth) ) Acrylates, polyfunctional (meth) acrylates such as bisphenol F epoxy di (meth) acrylate, etc., and one of these may be used alone, It may be used in combination with at least species.

  Among these, in particular, in applications where coating properties are required for the composition of the present invention, (meth) acryloylmorpholine, (meth) acrylic acid tetrahydrofurfuryl, (meth) acrylic acid benzyl, (meth) acrylic acid Such as cyclohexyl, trimethylcyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, mono (meth) acrylamide, etc. Monofunctional (meth) acrylates having a ring structure in the molecule are preferred. On the other hand, in applications where mechanical strength of the resulting cured product is required, 1,4-butanediol di (meth) acrylate and di (meth) ) 1,6-hexanediol acrylic acid, 1,9-nonanediodi (meth) acrylic acid Dipentaglycol di (meth) acrylate, tricyclodecane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Polyfunctional (meth) acrylates such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

  In the active energy ray-curable resin composition of the present invention, the total reaction in which the urethane (meth) acrylate oligomer (A) and the active energy ray reactive monomer other than the urethane (meth) acrylate oligomer (A) are combined. The content of the urethane (meth) acrylate oligomer (A) is preferably 40% by weight or more, more preferably 60% by weight or more, and the upper limit is usually 100% by weight relative to the amount of the sexual component. . If the content of the urethane (meth) acrylate oligomer (A) is not less than the above lower limit value, the curability will be good, and the three-dimensional workability will be improved without excessively increasing the mechanical strength of the cured product. This is preferable.

  Examples of the active energy ray-curable oligomer that may be contained in the active energy ray-curable resin composition of the present invention include epoxy (meth) acrylate oligomers and acrylic (meth) acrylate oligomers. Moreover, in the active energy ray-curable resin composition of the present invention, the active energy ray reaction other than the urethane (meth) acrylate oligomer (A) and the urethane (meth) acrylate oligomer (A) with respect to the total amount of the composition. The total amount of reactive components combined with the reactive monomer is preferably 60% by weight or more from the viewpoint of excellent curing speed and surface curability as a composition and no tack remains, and is 80% by weight or more. More preferably, it is particularly preferably 90% by weight or more, most preferably 95% by weight or more, while the upper limit is usually 100% by weight.

Polymerization initiator The polymerization initiator that may be contained in the active energy ray-curable resin composition of the present invention mainly improves the initiation efficiency of a polymerization reaction that proceeds by irradiation with active energy rays such as ultraviolet rays and electron beams. It is used for the purpose. As the polymerization initiator, a photo radical polymerization initiator that is a compound having a property of generating radicals by light is generally used, and any known photo radical polymerization initiator can be used as long as the effects of the present invention are not significantly impaired. It is. Furthermore, a combined system of a photo radical polymerization initiator and a photo sensitizer may be used.

  Specific examples of the radical photopolymerization initiator include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis (diethylamino) benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thioxanthone, diethylthioxanthone, Isopropylthioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, benzoin methyl Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoyl formate, 2-methyl-1- [ -(Methylthio) phenyl] -2-morpholinopropan-1-one, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2, 4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -Phenyl] -2-methyl-propan-1-one and the like.

  Among these, benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4,6, since the curing speed is high and the crosslinking density can be sufficiently increased. -Trimethylbenzoyldiphenylphosphine oxide and 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methyl-propan-1-one 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] Further preferred is 2-methyl-propan-1-one.

When the active energy ray-curable resin composition includes a compound having a radical polymerizable group and a cationic polymerizable group such as an epoxy group, the photo cationic polymerization initiator is used together with the above-described photo radical polymerization initiator. It may be included. The cationic photopolymerization initiator is not particularly limited, and any known one can be used as long as the effects of the present invention are not impaired.
These photopolymerization initiators can be used alone or in combination of two or more, and activities other than the urethane (meth) acrylate oligomer (A) and the urethane (meth) acrylate oligomer (A) according to the present invention. The amount is usually 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the energy ray-reactive monomer. It is preferable for the amount of the photopolymerization initiator to be not more than the above upper limit value because the mechanical strength is not easily lowered by the initiator decomposition product.

  Specific examples of the photosensitizer include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, Well-known things, such as 4-dimethylamino acetophenone, are mentioned. A photosensitizer may be used individually by 1 type and may be used in combination of 2 or more type.

Additives The active energy ray-curable resin composition of the present invention may contain additives as necessary as long as the effects of the present invention are not significantly impaired. Specifically, fillers such as glass fiber, glass bead, silica, alumina, calcium carbonate, mica, zinc oxide, titanium oxide, mica, talc, kaolin, metal oxide, metal fiber, iron, lead, metal powder; Carbon materials such as carbon fibers, carbon black, graphite, carbon nanotubes, fullerenes such as C60 (fillers and carbon materials are collectively referred to as inorganic components); antioxidants, heat stabilizers, ultraviolet absorbers, HALS, anti-fingerprint agent, surface hydrophilizing agent, antistatic agent, slipperiness imparting agent, plasticizer, mold release agent, antifoaming agent, leveling agent, antisettling agent, surfactant, thixotropy imparting agent, lubricant, flame retardant , Modifiers such as flame retardant aids, polymerization inhibitors, fillers, silane coupling agents; colorants such as pigments, dyes, hue modifiers, monomers or / and oligomers thereof, or inorganic components Curing agent required for the synthesis, catalyst, curing accelerators and the like can be mentioned, these auxiliary components may be used alone, or may be used in combination of two or more kinds.

  Among the additives, it is preferable to use silicone in order to impart slipperiness when the cured product is used and to improve wear resistance. Although there is no restriction | limiting in particular in the silicone to be used, It is preferable that a number average molecular weight is 1000 or more from a viewpoint that it is hard to bleed out and can maintain abrasion resistance long, The said urethane (meth) acrylate type oligomer ( From the aspect of compatibility with A), the number average molecular weight is preferably 3000 or less. Moreover, it is especially preferable to have an active energy ray reactive group.

  The active energy ray-reactive group preferably has at least one active energy ray-reactive group selected from the group consisting of a (meth) acryloyl group, an acryloyloxy group, and a vinyl group. Among them, a (meth) acryloyl group is preferable. It is preferable to have. These active energy ray-reactive groups may be introduced at any of the side chain, one end, both ends, and both ends of the side chain with respect to the silicone-based substituent. preferable.

  Known silicones can be used such as TEGO Rad 2200N, TEGO Rad 2500, TEGO Rad 2300 (manufactured by Degussa); Silaplane FM-0711, Silaplane FM-7711 (manufactured by Chisso); Commercially available products such as X-22-164A, KF-353, KF-355A, KF-6011 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK 333, BYK UV3500, BYK UV3570 (manufactured by BYK Chemie) can also be used.

  There is no limitation in particular as a method of making an active energy ray curable resin composition of this invention contain an additive etc., A conventionally well-known mixing, dispersion | distribution method, etc. are mentioned. In order to more reliably disperse additives and the like, it is preferable to perform a dispersion treatment using a disperser. Specifically, for example, two rolls, three rolls, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, seg barrier striker, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact mill And a method of treating with a kneader, a homogenizer, an ultrasonic disperser and the like.

  The amount of the urethane (meth) acrylate oligomer (A) relative to the total amount of the composition when the active energy ray-curable resin composition of the present invention contains components other than the urethane (meth) acrylate oligomer (A). Is more preferable in terms of elongation and film-forming property, and on the other hand, a smaller amount is preferable in terms of lowering the viscosity. Specifically, it is usually preferably 50% by weight or more, more preferably 70% by weight or more, and usually, it is preferably 100% by weight or less.

  The viscosity of the active energy ray-curable resin composition of the present invention can be adjusted as appropriate according to the application and use mode, but the viscosity at 25 ° C. in an E-type viscometer (rotor 1 ° 34 ′ × R24) is From the viewpoints of handleability, coatability, moldability, three-dimensional formability, etc., it is preferably 10 mPa · s or more, more preferably 100 mPa · s or more, and preferably 100000 mPa · s or less, more preferably 50000 mPa · s. It may be less than or equal to s. The adjustment of the viscosity of the active energy ray-curable resin composition can be adjusted by the types of the urethane (meth) acrylate oligomer (A) and the active energy ray-reactive monomer component and the blending ratio thereof.

  Depending on the coating method, the active energy ray-curable resin composition of the present invention can be diluted with an organic solvent to reduce the viscosity. Preferred solvents include toluene, xylene, ethyl acetate, butyl acetate, isopropanol, isobutanol, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone and the like, and usually 200 weights per 100 weight parts of the active energy ray curable resin composition. It can be used in less than part.

  As a coating method for the active energy ray-curable resin composition and a composition diluted with an organic solvent, a bar coater method, an applicator method, a curtain flow coater method, a roll coater method, a spray method, a gravure coater method, Known methods such as a comma coater method, a reverse roll coater method, a lip coater method, a die coater method, a slot die coater method, an air knife coater method, and a dip coater method can be applied. Among them, a bar coater method and a gravure coater are applicable. The method is preferred.

The active energy ray-curable resin composition of the present invention can be made into a cured film by irradiating this with active energy rays.
As the active energy rays used when the composition is cured, infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. From the viewpoint of apparatus cost and productivity, it is preferable to use an electron beam or an ultraviolet ray. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar Lasers, He—Cd lasers, solid lasers, xenon lamps, high frequency induction mercury lamps, sunlight, and the like are suitable.

When the irradiation amount of the active energy ray is cured by electron beam irradiation, the irradiation amount is preferably 1 to 10 Mrad. Moreover, in the case of ultraviolet irradiation, it is preferable that it is 50-1000 mJ / cm < ² >. The atmosphere during curing may be air, an inert gas such as nitrogen or argon. Moreover, you may irradiate in the sealed space between a film or glass, and a metal metal mold | die.
The thickness of the cured film of the present invention is appropriately determined according to the intended use, but the lower limit is preferably 1 μm, more preferably 3 μm, and particularly preferably 5 μm. The upper limit is preferably 200 μm, more preferably 100 μm, particularly preferably 50 μm, and most preferably 20 μm. When the film thickness is larger than the lower limit value, the appearance of design properties and functionality after three-dimensional processing becomes good. On the other hand, when the film thickness is smaller than the upper limit value, the internal curability and the three-dimensional workability are good, which is preferable.

Furthermore, the laminated body which has a layer which consists of a cured film of this invention on a base material can be obtained. The laminate of the present invention is not particularly limited as long as it has a layer comprising the cured film of the present invention, and a layer other than the substrate and the cured film of the present invention is interposed between the substrate and the cured film of the present invention. You may have / or it outside. Moreover, you may have multiple layers of the base material and / or the cured film of this invention.
As a method for obtaining the laminate of the present invention, all layers are laminated in an uncured state and then cured with active energy rays, and the lower layer is cured with active energy rays or semi-cured and then the upper layer is applied. A known method such as a method of curing with active energy rays again, a method of applying each layer to a release film or a base film, and then laminating the layers in an uncured or semi-cured state can be applied. In order to improve the adhesion between the layers, a method of curing with active energy rays after laminating in an uncured state is preferable. As a method of laminating in an uncured state, it is possible to apply a known method such as sequential coating in which the upper layer is applied after the lower layer is applied, or simultaneous multilayer coating in which two or more layers are simultaneously applied from multiple slits. However, this is not the case.

Specific examples of the base material include various plastics and metals such as polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polypropylene and polyester, nylon, polycarbonate, and (meth) acrylic resin.
The cured film of the present invention simultaneously has flexibility capable of following deformation during three-dimensional processing under high temperature conditions, elongation at break, mechanical strength, and stain resistance against general household contaminants such as ink and ethanol. The laminate of the present invention using the cured film of the present invention as a film on various substrates can be excellent in design and surface protection.

  The breaking elongation of the cured film of the present invention was determined by cutting the cured film of the present invention into a width of 10 mm and using a Tensilon tensile tester (Orientec, Tensilon UTM-III-100) at a temperature of 140 ° C. and a tensile rate. The value measured by performing a tensile test under the conditions of 50 mm / min and the distance between chucks of 50 mm is preferably 50% or more, more preferably 75% or more, and particularly preferably 100% or more, Most preferably, it is 150% or more.

  Contamination resistance of the cured film of the present invention is 75% by weight ethanol aqueous solution, red aqueous ink (pilot cartridge ink / red / IRF-12S-R) or blue aqueous (pilot ink cartridge ink / blue). Black / IRF-12S-BB) (hereinafter collectively referred to as contaminants) 0.03 g was dropped and contacted, and at room temperature (23 ° C.), in the case of a 75 wt% aqueous ethanol solution, 1 hour red aqueous ink Or in the case of blue water-based ink, after leaving still for 24 hours, the degree of contamination after wiping off contaminants with absorbent cotton containing water is visually evaluated. Here, the amount of contaminants after wiping is preferably a very small amount, more preferably so small that it is not visible.

  The cured film of the present invention and the laminate of the present invention can be used as a coating substitute film, and can be effectively applied to, for example, interior and exterior building materials, automobiles, home appliances, and other various members. is there.

Specific examples of the present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited by these examples unless it exceeds the gist.
Specific examples of the present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited by these examples unless it exceeds the gist.
<Calculation of molecular weight between calculation network cross-linking points>
The molecular weights between the calculated crosslinking points in each Example and Comparative Example are the number average molecular weight and mole number of the urethane acrylate oligomer and other active energy ray reactive monomers in the composition shown in Table 1, and the (meth) acryloyl group. It calculated from the number of functional groups. Moreover, the number average molecular weight of the urethane acrylate oligomer was calculated from the charged amount of each component as a raw material. Table 2 shows the calculation results. Here, the number average molecular weight of isobornyl acrylate used is 208, the number average molecular weight of N-vinylformamide is 71, the number average molecular weight of tricyclodecane diacrylate is 304, and the number average molecular weight of APG-700 is 1010. .

<Calculation method of urethane (meth) acrylate oligomer (A)>
The urethane (meth) acrylate oligomers of the examples and comparative examples were prepared by reacting components other than the component (a-3) under the condition that the isocyanate group becomes excessive to obtain an isocyanate-terminated urethane prepolymer. The urethane prepolymer and the component (a-3) were synthesized by a prepolymer method. Here, both ends of the obtained urethane (meth) acrylate oligomer are hydroxyalkyl (meth) acrylates. That is, 2 mol of hydroxyalkyl (meth) acrylate is added. Therefore, it calculated so that the molar ratio of hydroxyalkyl (meth) acrylate might be set to 2, and the average molecular weight was computed from the sum total of the product of the molecular weight of all the structural units, and molar ratio.
Table 1 shows the calculated number average molecular weight of the urethane (meth) acrylate oligomer and the number average molecular weight determined by GPC measurement as follows.

<Number average molecular weight measurement by GPC>
GPC (“HLC-8120GPC” manufactured by Tosoh Corporation), using THF as a solvent, polystyrene as a standard sample, TSKgel superH1000 + H2000 + H3000 as a column, a liquid feeding speed of 0.5 mL / min, a column oven temperature of 40 ° C., and number average The molecular weight was measured.

<Mechanical properties of cured film>
The cured film is cut to a width of 10 mm, and a tensile test is performed using a Tensilon tensile tester (Orientec, Tensilon UTM-III-100) at a temperature of 140 ° C., a tensile speed of 50 mm / min, and a chuck distance of 50 mm. And the elongation at break was measured. The results are shown in Table 1.

<Contamination resistance of cured film>
75% by weight ethanol aqueous solution, red aqueous ink (pilot cartridge ink / red / IRF-12S-R) or blue aqueous ink (pilot ink cartridge ink / blue black / IRF-12S-BB) (hereinafter, 0.03 g (collectively referred to as contaminants) was dropped and contacted at room temperature (23 ° C.) for 1 hour in the case of 75% by weight ethanol aqueous solution and 24 hours in the case of red aqueous ink or blue aqueous ink, respectively. After standing still, the degree of contamination after wiping off contaminants with absorbent cotton containing water was evaluated visually. The evaluation criteria are as follows.
○: Contaminant can be completely wiped Δ: Contaminant remains slightly ×: Contaminant remains remarkably

<Example 1>
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, (a-1) 274 g of isophorone diisocyanate, 84 g of 4,4′-methylenebis (cyclohexyl isocyanate), (a-2) 201 g of cyclohexanedimethanol was added, and 372 g of methyl ethyl ketone was further added and reacted for 9 hours while heating to 80 ° C. in an oil bath. After cooling to 60 ° C. after completion of the reaction, 0.18 g of dioctyltin dilaurate, 0.30 g of methylhydroquinone and 27 g of methyl ethyl ketone were added, and 41 g of hydroxyethyl acrylate was added dropwise as (a-3) to initiate the reaction. The reaction was carried out for 10 hours while heating to 70 ° C. in an oil bath, and the progress of the reaction was confirmed by a decrease in the peak derived from the isocyanato (NCO) group in the infrared absorption spectrum (hereinafter sometimes abbreviated as IR). Then, the end point of the reaction was confirmed by disappearance, and an active energy ray-curable resin composition was prepared.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 3,700. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 3700.
Next, the active energy ray-curable resin composition obtained with an applicator was applied onto a polyethylene terephthalate film to form a coating film, which was then dried at 60 ° C. for 1 minute, and an electron beam irradiation device (CB175, iGraphic). Manufactured) and irradiated with an electron beam under the conditions of an acceleration voltage of 165 kV and an irradiation dose of 5 Mrad, and then peeled from the polyethylene terephthalate film to obtain a cured film having a thickness of 100 μm.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 2>
Instead of 274 g of isophorone diisocyanate (a-1) and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate), (a-1) is 353 g of isophorone diisocyanate, and 201 g of cyclohexanedimethanol is 206 g as (a-2). An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that 372 g of methyl ethyl ketone, 373 g of dioctyltin dilaurate were changed to 0.16 g, and 0.30 g of methyl hydroquinone was changed to 0.26 g. .

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 3,700. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 3700.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 3>
As (a-1), 211 g of isophorone diisocyanate 274 g and 143 g of 4,4′-methylenebis (cyclohexyl isocyanate) 84 g, (a-2) 201 g of cyclohexanedimethanol 176 g, 354 g of methyl ethyl ketone, 354 g of methyl ethyl ketone, 27 g of methyl ethyl ketone An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that 46 g was used and 41 g of hydroxyethyl acrylate was changed to 70 g as (a-3).

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 2200. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 2200.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 4>
As (a-1), 274 g of isophorone diisocyanate was changed to 84 g and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate) as 40 g. As (a-2), 201 g of cyclohexanedimethanol was changed to 33 g, and 372 g of methyl ethyl ketone was changed to 380 g. Furthermore, 224 g of polycarbonate diol (Kuraray polyol C-1090, number average molecular weight 980, manufactured by Kuraray Co., Ltd.) was added as (a-5), and the reaction was performed at 80 ° C. for 9 hours in the same manner as in Example 1. Further, except that 0.18 g of dioctyltin dilaurate was 0.12 g, 0.32 g of methylhydroquinone was 0.12 g, 27 g of methyl ethyl ketone was 19 g, and 41 g of hydroxyethyl acrylate was changed to 19 g as (a-3). The reaction was carried out at 70 ° C. for 10 hours in the same manner as in 1. Then, 100 g of tricyclodecane diacrylate (IRR214K, manufactured by Daicel-Cytec) and 100 g of methyl ethyl ketone were added to prepare an active energy ray-curable resin composition.

The obtained active energy ray-curable resin composition had a calculated molecular weight between crosslinking points of 1200. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 5300.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 5>
As (a-1), isophorone diisocyanate 274 g was changed to 105 g, and 4,4′-methylenebis (cyclohexyl isocyanate) 84 g was changed to 50 g. As (a-2), cyclohexanedimethanol 201 g was changed to 41 g, and methyl ethyl ketone 372 g was changed to 476 g. Further, 280 g of polycarbonate diol (Kuraray polyol C-1090, number average molecular weight 980, manufactured by Kuraray Co., Ltd.) was added as (a-5), and the reaction was performed at 80 ° C. for 9 hours in the same manner as in Example 1. Example 1 except that 0.18 g of dioctyltin dilaurate was 0.15 g, 0.35 g of methylhydroquinone was 0.15 g, 27 g of methyl ethyl ketone was 24 g, and 41 g of hydroxyethyl acrylate was changed to 24 g as (a-3). In the same manner as above, an active energy ray-curable resin composition was prepared.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 5300. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 5300.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition E obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Comparative Example 1>
In a four-necked flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 292 g of isophorone diisocyanate (a-1) and 208 g of hydroxyethyl acrylate (a-3) were used, and dioctyltin dilaurate. 0.15 g, methylhydroquinone 0.25 g, and methyl ethyl ketone 500 g were added and reacted. The reaction is carried out for 10 hours while heating to 70 ° C. in an oil bath, the progress of the reaction is confirmed by the reduction of the peak derived from the NCO group in IR, the end point of the reaction is confirmed by disappearance, and the active energy ray curability is confirmed. A resin composition was prepared.

The obtained active energy ray-curable resin composition had a calculated molecular weight between crosslinking points of 450. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 450.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.

<Comparative example 2>
Instead of 274 g of isophorone diisocyanate and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate), (a-1) was changed to 357 g of isophorone diisocyanate, 201 g of cyclohexanedimethanol was changed to 217 g as (a-2), 383 g of methyl ethyl ketone was 383 g, dioctyltin An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that 0.18 g of dilaurate was changed to 0.15 g, 27 g of methyl ethyl ketone was changed to 17 g, and 41 g of hydroxyethyl acrylate was changed to 26 g as (a-3). did.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 6,300. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 6300.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Comparative Example 3>
In place of 274 g of isophorone diisocyanate and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate), (a-1) is changed to 408 g of isophorone diisocyanate, and in place of 201 g of cyclohexanedimethanol, (a-2) is changed to 151 g of 1,4-butanediol. An active energy ray-curable resin composition was prepared in the same manner as in Example 1 except that 372 g of methyl ethyl ketone was changed to 373 g and 0.18 g of dioctyltin dilaurate was changed to 0.15 g.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 3,700. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 3700.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition H obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Comparative Example 4>
(A-1) is replaced with 99 g of isophorone diisocyanate instead of 274 g of isophorone diisocyanate and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate), and (a-2) is replaced with 201 g of cyclohexanedimethanol and 29 g of 1,9-nonanediol. Then, 372 g of methyl ethyl ketone was changed to 373 g, and 179 g of polycarbonate diol (Kuraray polyol C-1090, number average molecular weight 980, manufactured by Kuraray Co., Ltd.) was added as (a-5), and at 80 ° C. for 9 hours as in Example 1. The reaction was performed. Further, the same procedure as in Example 1 was conducted except that 0.18 g of dioctyltin dilaurate was changed to 0.09 g, 0.30 g of methylhydroquinone was changed to 0.06 g, and 41 g of hydroxyethyl acrylate was changed to 22 g as (a-3). The reaction was carried out at 10 ° C. for 10 hours. Next, 210 g of isobornyl acrylate (IB-XA, manufactured by Kyoei Chemical Co., Ltd.) and 60 g of N-vinylformamide (NVF-P, manufactured by Daianitrix) were added to prepare an active energy ray-curable resin composition.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 5200. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 3700.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 6>
As (a-1), 174 g of isophorone diisocyanate was changed to 103 g, and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate) was changed to 61 g. As (a-2), 201 g of cyclohexanedimethanol was changed to 33 g, and 372 g of methyl ethyl ketone was changed to 422 g. Further, 225 g of polycarbonate diol (Kuraray polyol C-1090, number average molecular weight 980, manufactured by Kuraray Co., Ltd.) was added as (a-5), and the reaction was performed at 80 ° C. for 9 hours in the same manner as in Example 1. Further, except that 0.18 g of dioctyltin dilaurate was 0.14 g, 0.30 g of methylhydroquinone was 0.24 g, 27 g of methyl ethyl ketone was 54 g, and 41 g of hydroxyethyl acrylate was changed to 54 g as (a-3). The reaction was carried out at 70 ° C. for 10 hours in the same manner as in No. 1, and then 5 g of silicone (Silane Plain FM-7711, manufactured by Chisso Corporation), 10 g of ultraviolet absorber (Tinuvin 328, manufactured by Ciba Specialty Chemicals), HALS (Tinuvin 144, 10 g of Ciba Specialty Chemicals) and 24 g of methyl ethyl ketone were added to prepare an active energy ray-curable resin composition.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 2100. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 2100.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 7>
(A-1) is changed to 84 g of isophorone diisocyanate and 160 g of 4 isophorone diisocyanate, 201 g of cyclohexanedimethanol is changed to 43 g, (a-2) is changed to 43 g of methylethylketone, and 446 g is changed to (a-5), and polycarbonate diol (PCDX) is changed. -55, number average molecular weight 830, manufactured by Asahi Kasei Co., Ltd.) 244 g was added, and the reaction was carried out at 80 ° C. for 9 hours in the same manner as in Example 1. Example 1 except that 0.18 g of dioctyltin dilaurate was 0.14 g, 0.34 g of methylhydroquinone was 0.24 g, 27 g of methyl ethyl ketone was 30 g, and 41 g of hydroxyethyl acrylate was changed to 30 g as (a-3). In the same manner as above, the reaction was carried out at 70 ° C. for 10 hours, and then 5 g of silicone (Silane Plain FM-7711, manufactured by Chisso Corporation), 10 g of ultraviolet absorber (Tinuvin 328, manufactured by Ciba Specialty Chemicals), HALS (Tinubin 144, Ciba) 10 g of Specialty Chemicals) and 48 g of methyl ethyl ketone were added to prepare an active energy ray-curable resin composition.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 3,700. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 3700.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.
The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1.

<Example 8>
As (a-1), 274 g of isophorone diisocyanate was changed to 84 g and 84 g of 4,4′-methylenebis (cyclohexyl isocyanate) as 50 g. As (a-2), 201 g of cyclohexanedimethanol was changed to 36 g, and 372 g of methyl ethyl ketone was changed to 407 g. Further, 236 g of polycarbonate diol (Duranol T4691, number average molecular weight 1060, manufactured by Asahi Kasei Co., Ltd.) was added as (a-5), and the reaction was carried out at 80 ° C. for 9 hours in the same manner as in Example 1. Example 1 except that 0.18 g of dioctyltin dilaurate was 0.14 g, 0.34 g of methylhydroquinone was 0.24 g, 27 g of methyl ethyl ketone was 22 g, and 41 g of hydroxyethyl acrylate was changed to 22 g as (a-3). In the same manner as above, the reaction was carried out at 70 ° C. for 10 hours, then 48 g of bifunctional acrylate (APG-700, number average molecular weight 1010, manufactured by Shin-Nakamura Chemical), 5 g of silicone (Silaplane FM-7711, manufactured by Chisso Corporation), An ultraviolet ray absorbent (Tinuvin 460, manufactured by Ciba Specialty Chemicals) 10 g, HALS (Tinuvin 144, manufactured by Ciba Specialty Chemicals) 10 g, and methyl ethyl ketone 71 g were added to prepare an active energy ray-curable resin composition.

The obtained active energy ray-curable resin composition had a molecular weight between calculated network crosslinking points of 2900. Moreover, the number average molecular weight of the urethane acrylate part calculated | required by GPC was 4500.
Next, a cured film was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition obtained as described above was used.

  The obtained cured film was evaluated for mechanical properties and stain resistance. The results are shown in Table 1. The calculation results of the molecular weight of urethane acrylate are summarized in Table 2.

When the active energy ray-curable resin composition of the present invention is cured to form a cured film, the flexibility, elongation at break, mechanical strength capable of following deformation during three-dimensional processing under high temperature conditions, In addition, a cured film having stain resistance against general household contaminants such as ink and ethanol can be provided at the same time, and by using the cured film as a coating on various substrates, it is possible to impart designability or surface protection. it can.
Thereby, the laminated body which has the cured film which consists of an active energy ray-curable resin composition of this invention, or the layer which consists of this cured film can be used as a coating substitute film, for example, a building material for interior and exterior, It can be effectively applied to various members such as automobiles and home appliances.

Claims (7)

At least (a-1) a polyisocyanate and (a-2) a low molecular weight polyol having an alicyclic structure and a number average molecular weight of 500 or less are reacted so that an isocyanate group is excessive, thereby obtaining an isocyanate-terminated urethane prepolymer. Then , an active energy ray-curable resin composition comprising a urethane (meth) acrylate oligomer (A) obtained by reacting the isocyanate-terminated urethane prepolymer with (a-3) hydroxyalkyl (meth) acrylate , (a-2) as the number average molecular weight of 500 or lower molecular weight polyol having an alicyclic structure includes 1,4-cyclohexanedimethanol, and between calculated network crosslinking points in the active energy ray curable resin sets Narubutsu molecular weight Is an active energy, characterized by being from 1000 to 6000 Curable resin composition.   The active energy ray-curable resin composition according to claim 1, wherein the (a-1) polyisocyanate includes a polyisocyanate having an alicyclic structure. The total amount of the three components (a-1) polyisocyanate, (a-2) a low molecular weight polyol having an alicyclic structure and a number average molecular weight of 500 or less, and (a-3) hydroxyalkyl (meth) acrylate is 100.0 mol. % (A-2) a low molecular weight polyol having an alicyclic structure and having a number average molecular weight of 500 or less is from 15.0 mol% to 42.5 mol%, and (a-3) hydroxyalkyl The active energy ray-curable resin composition according to claim 1 or 2, wherein the (meth) acrylate is 7.5 mol% or more and 35.0 mol% or less .   The (a-1) polyisocyanate includes a polyisocyanate in which the alicyclic structure of the polyisocyanate is a six-membered ring structure, and the six-membered ring structure between the isocyanato groups is bonded by 1,4-position substitution. Or the active energy ray-curable resin composition according to 3;   The active energy according to any one of claims 1 to 4, wherein the urethane (meth) acrylate-based oligomer (A) is a reaction product further comprising a high molecular weight polyol having a number average molecular weight of more than (a-5) 500. A linear curable resin composition.   The cured film formed by irradiating an active energy ray curable resin composition of any one of Claims 1-5 with an active energy ray.   The laminated body which has a layer which consists of a cured film of Claim 6 on a base material.